WO2006077022A2 - Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird - Google Patents

Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird Download PDF

Info

Publication number
WO2006077022A2
WO2006077022A2 PCT/EP2006/000120 EP2006000120W WO2006077022A2 WO 2006077022 A2 WO2006077022 A2 WO 2006077022A2 EP 2006000120 W EP2006000120 W EP 2006000120W WO 2006077022 A2 WO2006077022 A2 WO 2006077022A2
Authority
WO
WIPO (PCT)
Prior art keywords
oil
monoglycerides
reaction
water
additive
Prior art date
Application number
PCT/EP2006/000120
Other languages
German (de)
English (en)
French (fr)
Other versions
WO2006077022A3 (de
Inventor
Ulrich SCHÖRKEN
Sabine Both
Frank Bongardt
Diana Stuhlmann
Original Assignee
Cognis Ip Management Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Ip Management Gmbh filed Critical Cognis Ip Management Gmbh
Priority to AT06703801T priority Critical patent/ATE470720T1/de
Priority to JP2007551578A priority patent/JP4989489B2/ja
Priority to BRPI0606620-8A priority patent/BRPI0606620B1/pt
Priority to US11/813,939 priority patent/US7935508B2/en
Priority to CA2595235A priority patent/CA2595235C/en
Priority to EP06703801A priority patent/EP1838861B1/de
Priority to DE502006007160T priority patent/DE502006007160D1/de
Publication of WO2006077022A2 publication Critical patent/WO2006077022A2/de
Publication of WO2006077022A3 publication Critical patent/WO2006077022A3/de

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6472—Glycerides containing polyunsaturated fatty acid [PUFA] residues, i.e. having two or more double bonds in their backbone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/44—Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention is in the field of glycerides and relates to a process for the preparation of monoglycerides by enzymatic catalysis and their use.
  • hydrolases especially lipases (EC 3.1.1.3) are used for fat cleavage even in large-scale processes.
  • lipases EC 3.1.1.3
  • the classical chemical method of monoglyceride production proceeds via a base-catalyzed glycerolysis of triglycerides, typically giving a yield of 40-60% monoglyceride relative to the total glycerides. Further enrichment up to> 90% monoglyceride content is achieved by physical separation methods such as molecular distillation or crystallization.
  • WO9013656 and WO9004033 describe the preparation of monoglycerides via enzymatic alcoholysis with various alcohols and a little water in the batch. Lipases are used in powder form or immobilized. In the examples, lipases are used in about 20% by weight, based on the triglyceride, and the alcohol component in 20 times the excess.
  • WO9116441, WO9116442 and US5116745 describe processes in which, in the presence of a solvent, an alcohol and an aqueous buffer, mixed regioselective alcoholysis and hydrolysis to 1,2-diglycerides and 2-monoglycerides is carried out using lipases.
  • EP407959 describes a process for the preparation of monoesters by a thermostable immobilized " lipase in the presence of " secondary or tertiary alcohols as a solution " mediator.
  • WO02O6505 (Nippon Suisan Kaisha Ltd) describes regioselective lipase-immobilized alcoholysis with high alcohol excess and high enzyme use concentration, followed by reesterification of the monoglyceride.
  • JP03108489 and JP03187385 (Meito Sangyo Co. Ltd.) describe the regioselective hydrolysis of triglycerides with alkaline lipase with the addition of alkaline salts. It is a lipase that is active only under alkaline conditions.
  • JP03103499 (Meito Sangyo Co. Ltd.) describes the regioselective alcoholysis of PUFA triglycerides with isobutanol in the presence of an alkaline lipase.
  • the enzymatic production of monoglycerides has been described many times, but in all the above documents, solvents are needed, the water of reaction must be removed consuming or the lipases are very special or immobilized. Due in part to low reaction rates compared to classical chemical synthesis, long reaction times and thus high capacity utilization or high concentrations of alcohol or lipase to be reacted are required in order to obtain a higher yield of desired monoglycerides.
  • the object of the present invention has now been to find a cost-effective variant to increase the yield of monoglycerides of polyol esters such as triglycerides in enzymatic alcoholysis and to keep the content of enzyme as low as possible.
  • the invention relates to a process for the preparation of monoglycerides, in which triglycerides are enzymatically reacted in the presence of linear or branched alcohols having a number of carbon atoms of 1-8 carbon atoms with an esterase which is activated by the addition of alkaline salts.
  • a triglyceride is cleaved in the presence of an alcohol into a 2-monoglyceride and two fatty acid esters.
  • the reaction can be carried out by the use of small amounts of esterase, preferably lipase very cost.
  • the reaction is carried out directly with the enzyme concentrate with the addition of an alkaline inorganic salt which causes strong activation of the enzyme. As a result, good conversion is achieved with low enzyme dosage even without stabilization of the enzyme by immobilization. An addition of solvents is not necessary.
  • the alcoholysis is carried out at temperatures of 10 ° to 40 ° C, preferably at 10 ° to 3O 0 C and particularly preferably at a temperature of 15 ° to 25 ° C.
  • the reaction is carried out at a water content of 0.1-10% by weight, preferably 0.1-5% by weight and more preferably 0.1-2% by weight, based on the amount of triglyceride, the Water content of the liquid enzyme preparation is included.
  • the reaction works well at higher water contents, but then the content of formed free fatty acid is increased.
  • the free fatty acid is not desired since it can undergo a re-esterification in the distillative separation of ester and glyceride mixture and thus reduces the yield of monoglyceride.
  • the reaction time is according to the invention preferably 12-48 h, depending on the enzyme concentration used. Preferably, all reactants are mixed and the reaction started by addition of the enzyme preparation.
  • the addition of the alcohol component preferably methanol and / or ethanol, preferably ethanol, is carried out either completely at the beginning or metered over the reaction period.
  • the amount of alcohol used is variable, minimum 2 moles of alcohol to 1 mole of oil, maximum 75 wt .-% alcohol and 25 wt .-% oil in the batch.
  • the esterase is deactivated by heat, and the precipitated esterase is then optionally filtered off, wherein in addition to the precipitated esterase the removal of additives or formulation constituents of the enzyme preparation used can be achieved.
  • the alcohol component can be removed by distillation, for example, at 80 ° C and 100 mbar vacuum and a mixture of alkyl ester and monoglyceride is obtained.
  • the alkyl esters and monoglycerides can be separated by distillation in a next step, for example via a thin-film evaporator or via a column. Reaction conditions are for example at 175 ° C and 0.3 mbar vacuum. The monoglyceride remains in the sump.
  • the esterases to be used in the process according to the invention are preferably those derived from an organism selected from the group formed by Thermomyces lanugenosus, Candida antarctica A, Candida antarctica B, Rhizomucor miehei, Candida cylindrace / Rhizopus javü ⁇ icus, Porcine pancreas, Aspergillus n 'strength, Candida ru- gosa, Mucor javanicus, Pseudomonas fluorescens, Rhizopüs oryzae, Pseudomonas sp., chromogen mobacterium viscosum, Fusarium oxysporum and Penicillium came Berti.
  • esterases from Thermomyces lanugenosus with the synonym: H ⁇ micola lanuginosa.
  • Esterases are enzymes that catalyze the formation and hydrolysis of esters; as hydrolases, they split their respective substrates by incorporating the elements of the water.
  • the esterases include, for example, the lipolytic lipases which are preferred esterases according to the invention.
  • Particularly preferred for the process according to the invention is the use of 1,3-regiospecific lipases, which are characterized by the fact that they preferentially split off the fatty acids at the 1- and 3-position of triglycerides.
  • any 1,3-regioselective lipase or esterase can be used in free or immobilized form for the process according to the invention.
  • the lipase of Thermomyces lanugenosus manufactured by Novozymes, name Lipozyme TL 100 1 or Lipolase 100 EX
  • Experimental data has shown that the addition of small amounts of alkaline inorganic salts dramatically increases the enzyme activity of the esterases.
  • non-immobilized lipases are activated by the alkaline salts.
  • a use concentration of 0.05-2% of the commercially available liquid preparation is used in relation to the amount of triglyceride used.
  • These commercially available enzyme liquid preparations have an average enzyme activity of 100,000 U / ml.
  • An enzyme unit U is defined as the amount of enzyme that converts a micromole substrate per 5 minutes.
  • the activation of the esterase is preferably carried out using alkaline inorganic salts selected from the group formed by hydroxides, carbonates and phosphates of sodium, potassium, calcium, magnesium and ammonium, predissolved in water.
  • alkaline inorganic salts selected from the group formed by hydroxides, carbonates and phosphates of sodium, potassium, calcium, magnesium and ammonium, predissolved in water.
  • Activation of the esterases according to the invention is between 0.00001 and 1 wt .-%, preferably between 0.0001 and 0.2 wt .-% based on the amount of triglyceride.
  • the amount of basic additive used depends on the amount of enzyme liquid preparation used which is buffered and on the strength of the base. When using NaOH and ⁇ 0.5% enzyme-liquid preparation, the use concentration in the lower concentration
  • a measurement of the pH of the reacted product mixture also shows that the pH is in the neutral to weakly acidic, which makes an enzyme activation alone via pH shift unlikely.
  • the process according to the invention preferably employs triglycerides of fats and oils 35 which have a high content of monounsaturated and / or polyunsaturated fatty acids and are selected from the group formed from sunflower oil, rapeseed oil, disperse oil, soybean oil, linseed oil, peanut oil, tallow, olive oil, castor oil, palm oil and used oils such as used cooking fat.
  • Peanut oil contains on average (based on fatty acid) 54% by weight of oleic acid, 24% by weight of linoleic acid, 1% by weight of linolenic acid, 1% by weight of arachidic acid, 10% by weight of palmitic acid, and 5% by weight. % Stearic acid.
  • the melting point is 2 to 3 ° C.
  • Linseed oil typically contains 5% by weight of palmitic, 4% by weight of stearic, 22% by weight of oil, 17% by weight of linoleic acid and 52% by weight of linolenic acid.
  • the iodine number is in the range of 155 to 205, the saponification number is 188 to 196 and the melting point is about - 20 ° C.
  • Olive oil contains predominantly oleic acid. Palm oil contains about 2 fatty acid components
  • Rapeseed oil typically contains about 48% by weight of erucic acid, 15% by weight of oleic acid, 14% by weight of linoleic acid, 8% by weight of linolenic acid, 5% by weight of icosenoic acid, 3% by weight of palmitic acid, 2% by weight of fatty acid components % Hexadecenoic acid and 1% by weight docosadienoic acid.
  • rapeseed oil typically contains about 48% by weight of erucic acid, 15% by weight of oleic acid, 14% by weight of linoleic acid, 8% by weight of linolenic acid, 5% by weight of icosenoic acid, 3% by weight of palmitic acid, 2% by weight of fatty acid components % Hexadecenoic acid and 1% by weight docosadienoic acid.
  • rapeseed oil typically contains about 48% by weight of erucic acid, 15% by weight of ole
  • Typical fatty acid moieties here are erucic acid 0.5% by weight, oleic acid 63% by weight, linoleic acid 20% by weight, linolenic acid 9,% by weight, icosenoic acid 1% by weight, palmitic acid 4% by weight, hexadecenoic acid 2 wt .-% and docosadienoic 1 wt .-%.
  • Castor oil consists of 80 to 85 wt .-% of the glyceride of ricinoleic acid, besides are to., 20. , about 7 wt .-%, glycerides of. Oil, to 3% by weight glycerides of linoleic and to about 2% by weight
  • Soybean oil contains 55 to 65 wt .-% of the total fatty acids polyunsaturated acids, and in f - special linoleic and linolenic acid. The situation is similar .
  • sunflower oil whose typical fatty acid spectrum, based on total fatty acid, is as follows: about 1% by weight
  • alcohol components which have a number of carbon atoms of 1-8 C atoms. These may preferably be primary or secondary alcohols. Ethanol or 1-propanol are used as the preferred alcohol component.
  • the content of alcohol is preferably from 10 to 75% by weight, based on the triglyceride used, preference is given to 15 to 40 wt .-% used.
  • the monoglyceride content depends on the amount of alcohol used.
  • the alcohol can be removed, preferably via distillation.
  • This additional process step gives monoglycerides mixed with alkyl esters which can be used in the mixture as a lubricant additive, as an additive for fuels or as an emulsifying constituent in foods, cosmetic and / or pharmaceutical formulations.
  • another object of the invention is the use of monoglycerides in the mixture with the alkyl esters contained in the reaction mixture as a lubricant additive, as an additive for fuels or as an emulsifying ingredient in food, cosmetic and / or pharmaceutical formulations.
  • the alkyl esters can be separated from the monoglycerides, preferably via distillation.
  • This additional process step gives monoglycerides which can be used as a lubricant additive, as an additive for fuels or as an emulsifying constituent in foods, cosmetic and / or pharmaceutical formulations.
  • a further subject of the invention is the use of monoglycerides prepared by the process according to the invention after separation of the alcohol and the alkyl esters as emulsifier in food, cosmetic and / or pharmaceutical formulations
  • Another object of the invention is the use of monoglycerides prepared by the process according to the invention in the mixture with alcohol and alkyl ester as a lubricant additive or as an additive for fuels.
  • the process according to the invention makes it possible to use the regiospecific fatty acid composition of the naturally occurring oils.
  • the monoglyceride fraction mainly contains the fatty acid composition found in the 2-position of the oils. Both Most naturally occurring oils are the more highly unsaturated fatty acids bound in the 2-position.
  • Based on palm oil for example, a monoglyceride with a high content of oleic acid can be obtained, which is particularly suitable for use in foods or cosmetics.
  • monoglycerides in the food industry is also known from the literature. According to EC directives, the content of monoglycerides and diglycerides must be at least 70%, the acid value must not exceed 6, the product must not contain more than 7% free glycerol and 2% water. Monoglycerides with> 90% mono- and diester and> 70% monoester content are achieved via the enzymatic process coupled with distillative removal of the fatty acid esters. The maximum values for water content, free glycerol and acid number are well below. Thus, the use of monoglycerides prepared by the process according to the invention in the food industry is given.
  • monoglycerides in cosmetic or pharmaceutical formulations is also known from the literature.
  • the monoglycerides prepared according to the invention with> 90% monoester and diester and> 70% monoester content can be used as W / O emulsifiers, coemulsifiers, restoring components, consistency factors or consistency adjusters in creams, lotions, ointments, surfactant preparations and in cosmetic and pharmaceutical waters in oil (W / O) and oil in water (OfW) emulsions.
  • Imrnobilisate of the approaches 1 - 3, and 15 + 16 were purchased directly from the manufacturer in immobilized form.
  • the immobilizates of batches 4 to 8 were prepared by adsorption on Ac-curel MP 1000 (Membrana).
  • 1 Accurel MP 1000 was incubated for 1 h in 10 ml of ethanol. After decanting the ethanol "IO g water were and 0.5 g of lipase were added. The mixture was incubated overnight at room temperature. The mixture was then separates the immobilized via filtration and dried for 24 h on sheets of paper at room temperature.
  • Immobilization of Lipolase on Accurel MP 1000 (Membrana): 5 g of MP1000 were placed in a 250 ml Erlenmeyer flask and 15 ml of ethanol was added. The mixture was shaken for 1 h, then ethanol was decanted off. To the MP1000 was added 50 grams of water. After stirring for 1 h, the water was decanted off. 100 ml of phosphate buffer, 20 mM, pH 6.0 was added and the immobilization started by addition of 5 g lipolase liquid preparation. The mixtures were stirred overnight at 8 ° C, then the enzyme immobilizate was filtered off. The immobilizate was dried overnight between paper towels at room temperature.
  • the immobilizate was weighed out and used for the alcoholysis, an enzyme-rich mixture corresponding to 0.2 g lipolase liquid preparation.
  • the content of glycerides and esters was analyzed by gas chromatography. The evaluation was carried out over area percent, whereby the excess free alcohols were not included. Samples were taken at the times indicated in the table.
  • the content of glycerides was analyzed by gas chromatography. The evaluation was carried out over area percent. The glycerol content was also analyzed by gas chromatography and is reported in uncalibrated area percent. According to mass balance, the absolute glycerol content is lower, but here the comparison of the relative values is decisive.
  • GC samples were taken for glycerol determination after 16 h and for glyceride determination after 40 h of reaction time. Acid numbers were determined after 16 h.
  • reaction rate was reduced with an increase in the alcohol content.
  • the reaction rate could be improved so that good monoglyceride formation is achieved even with a high molar excess of ethanol (batch 6).
  • the optimum reaction temperature is in the range of 20-25 0 C.
  • Example 10 Alcoholysis of sunflower oil and distillative enrichment of the monoglyceride
  • the mixture was stirred for 30 min at 80 0 C, then for one hour under vacuum at 80 0 C stirred to residual water from the After the reaction mixture had vented to atmospheric pressure, the mixture was filtered while warm, and a sample was taken for gas chromatographic analysis The batch was then separated by short path distillation.
  • the reaction parameters are 180 0 C and 0.5 mbar at adef ⁇ ngertemperatur of 25 0 C and a reference temperature of 80 0 C.
  • a mass balance of the distillation gave 29.8 wt .-% bottom product and 70.2 wt .-% distillate.
  • the monoglyceride-containing bottom product was subjected to gas chromatographic analysis.
  • Example 11 Alcoholysis of new sunflower oil and distillative enrichment of the monoglyceride
  • the mixture was stirred for 30 min at SO ° C, followed by a de STUN under vacuum at 80 ° C was stirred for ⁇ to residual water from the reaction mixture to remove. After relaxation of the reaction mixture to normal pressure, the mixture was filtered while warm. A sample was taken for gas chromatographic analysis. The batch was then separated via short path distillation.
  • the reaction parameters are 180 0 C and 0.5 mbar at a cold finger temperature of 25 0 C and a pot temperature of 80 0 C.
  • the bottom product Monogly- cerid containing a gas chromatographic analysis has been subjected.
  • Example 12 Alcoholysis of safflower oil and distillative enrichment of the monoglyceride
  • the emulsifying property of the enzymatically prepared and distilled monoglycerides is studied in a system of 80% water and 20% oil.
  • the oils Myritol 312 (Medium Chain Triglyceride) and paraffin oil are used.
  • the comparison substance used is a molecularly distilled monoglyceride (Monomuls 90 O) with a Mohöglyceridgehalt of> 90%.
  • the emulsifying properties in the system Myritol 312 / water are determined at active substance concentrations of 1%, 2.5% and 5%.
  • the emulsifying properties in the paraffin oil / water system are determined at active substance concentrations of 1%, and 5%.
  • the type of emulsion formed is determined by conductivity measurement. Studies are carried out on the monoglyceride mixtures of Examples 9, 10 and 11. Emulsion formation in the system Myritol 312 / water
  • Lubricating properties were measured by HFFR (High Frequency Reciprocating Rig Test) according to CEC Method F-06-T-94.
  • HFFR High Frequency Reciprocating Rig Test
  • Various diesel fuels and monoglyceride mixtures based on sunflower oil and rapeseed oil were used as shown in the table below.
  • Example 16 Examination of the fatty acid composition of monoglyceride from sunflower oil
  • the monoglyceride fraction or the distillate fraction from Example 10 are analyzed by gas chromatography for their fatty acid composition and compared with the starting material sunflower oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Genetics & Genomics (AREA)
  • Microbiology (AREA)
  • General Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Combustion & Propulsion (AREA)
  • Emergency Medicine (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Fats And Perfumes (AREA)
  • Edible Oils And Fats (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
PCT/EP2006/000120 2005-01-19 2006-01-10 Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird WO2006077022A2 (de)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AT06703801T ATE470720T1 (de) 2005-01-19 2006-01-10 Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird
JP2007551578A JP4989489B2 (ja) 2005-01-19 2006-01-10 アルカリ塩により活性化されたＴｈｅｒｍｏｍｙｃｅｓｌａｎｕｇｉｎｏｓｕｓリパーゼを用いたアルコール処理による、トリグリセリドからのモノグリセリドの製造方法および使用
BRPI0606620-8A BRPI0606620B1 (pt) 2005-01-19 2006-01-10 "process for the preparation of monoglycerides".
US11/813,939 US7935508B2 (en) 2005-01-19 2006-01-10 Production and use of monoglycerides
CA2595235A CA2595235C (en) 2005-01-19 2006-01-10 Production and use of monoglycerides
EP06703801A EP1838861B1 (de) 2005-01-19 2006-01-10 Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird
DE502006007160T DE502006007160D1 (de) 2005-01-19 2006-01-10 Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005002711.3 2005-01-19
DE102005002711A DE102005002711A1 (de) 2005-01-19 2005-01-19 Herstellung und Verwendung von Monoglyceriden

Publications (2)

Publication Number Publication Date
WO2006077022A2 true WO2006077022A2 (de) 2006-07-27
WO2006077022A3 WO2006077022A3 (de) 2007-01-11

Family

ID=36650497

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/000120 WO2006077022A2 (de) 2005-01-19 2006-01-10 Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird

Country Status (9)

Country Link
US (1) US7935508B2 (pt)
EP (1) EP1838861B1 (pt)
JP (1) JP4989489B2 (pt)
AT (1) ATE470720T1 (pt)
BR (1) BRPI0606620B1 (pt)
CA (1) CA2595235C (pt)
DE (2) DE102005002711A1 (pt)
ES (1) ES2346686T3 (pt)
WO (1) WO2006077022A2 (pt)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2006389A2 (en) * 2006-04-13 2008-12-24 Nippon Suisan Kaisha, Ltd. Method for production of condensed polyunsaturated fatty acid oil
JP2009153485A (ja) * 2007-12-27 2009-07-16 Maruha Nichiro Seafoods Inc 高度不飽和脂肪酸の濃縮方法
WO2009124844A2 (en) * 2008-04-07 2009-10-15 Novozymes A/S Method for producing monounsaturated glycerides
JP2013121366A (ja) * 2013-02-13 2013-06-20 Maruha Nichiro Seafoods Inc 高度不飽和脂肪酸の濃縮方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010118891A1 (de) * 2009-04-17 2010-10-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Schmierflüssigkeit sowie verfahren zur herstellung derselben
WO2017006876A1 (ja) * 2015-07-03 2017-01-12 関西化学機械製作株式会社 脂肪酸エステルの製造方法
CN111492044B (zh) * 2017-10-13 2024-04-12 格雷科斯生物股份有限公司 制备甘油单酯油的方法以及含有甘油单酯油的食物产品
GB201817589D0 (en) * 2018-10-29 2018-12-12 Castrol Ltd Lubricant compositions
CN111378700A (zh) * 2020-02-24 2020-07-07 广东聚石化学股份有限公司 一种山茶油脂肪酸酯的制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60102192A (ja) * 1983-11-10 1985-06-06 Meito Sangyo Kk モノグリセライドの製造法
WO1990004033A1 (en) * 1988-10-04 1990-04-19 Enzytech, Inc. Production of monoglycerides by enzymatic transesterification
JPH03103499A (ja) * 1989-09-14 1991-04-30 Meito Sangyo Kk 高度不飽和脂肪酸モノグリセリドの製造方法
JPH03108489A (ja) * 1989-09-22 1991-05-08 Meito Sangyo Kk 長鎖高度不飽和脂肪酸モノグリセリドの製造法
JPH03187385A (ja) * 1983-11-10 1991-08-15 Meito Sangyo Kk モノグリセライドの製造法
WO1991016442A1 (en) * 1990-04-19 1991-10-31 The Procter & Gamble Company Regio and stereoselective synthesis of triglycerides
FR2772391A1 (fr) * 1997-12-15 1999-06-18 Toulousaine De Rech Et De Dev Procede d'alcoolyse enzymatique d'une huile de tournesol oleique, notamment pour la fabrication d'une composition lubrifiante tensioactive
EP1300470A1 (en) * 2000-07-13 2003-04-09 Nippon Suisan Kaisha, Ltd. Process for the prodcution of glycerides with lipases
WO2006077023A2 (de) * 2005-01-19 2006-07-27 Cognis Ip Management Gmbh Zusammensetzungen verwendbar als biotreibstoff

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5316927A (en) 1988-10-04 1994-05-31 Opta Food Ingredients, Inc. Production of monoglycerides by enzymatic transesterification
JPH02160984A (ja) * 1988-12-09 1990-06-20 Novo Ind As 古紙の脱インキ方法
US5935828A (en) 1989-05-01 1999-08-10 Opta Food Ingredients, Inc. Enzymatic production of monoglycerides containing omega-3 unsaturated fatty acids
EP0407959A3 (en) 1989-07-11 1992-01-02 Lion Corporation Process for producing polyol fatty acid monoesters
US5149642A (en) 1990-04-20 1992-09-22 The Procter & Gamble Company Process for preparing 2-acylglycerides or 1,2 or 2,3-diacylglycerides
GB9315205D0 (en) 1993-07-22 1993-09-08 Exxon Chemical Patents Inc Additives and fuel compositions
US5714373A (en) * 1995-02-27 1998-02-03 Recombinant Biocatalysis, Inc. Thermococcus AV4 and enzymes produced by the same
JPH1049072A (ja) * 1996-08-06 1998-02-20 Hitachi Ltd ガス放電型表示装置とその製造方法
WO2000063322A1 (en) 1999-04-21 2000-10-26 Pure Fuels Usa, Inc. Fuel compositions
EP1088880A1 (en) 1999-09-10 2001-04-04 Fina Research S.A. Fuel composition
EP1270734B1 (de) * 2001-06-21 2007-12-12 T + T Oleochemie GmbH Verfahren zur enzymatischen Spaltung von Ölen und Fetten

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60102192A (ja) * 1983-11-10 1985-06-06 Meito Sangyo Kk モノグリセライドの製造法
JPH03187385A (ja) * 1983-11-10 1991-08-15 Meito Sangyo Kk モノグリセライドの製造法
WO1990004033A1 (en) * 1988-10-04 1990-04-19 Enzytech, Inc. Production of monoglycerides by enzymatic transesterification
JPH03103499A (ja) * 1989-09-14 1991-04-30 Meito Sangyo Kk 高度不飽和脂肪酸モノグリセリドの製造方法
JPH03108489A (ja) * 1989-09-22 1991-05-08 Meito Sangyo Kk 長鎖高度不飽和脂肪酸モノグリセリドの製造法
WO1991016442A1 (en) * 1990-04-19 1991-10-31 The Procter & Gamble Company Regio and stereoselective synthesis of triglycerides
FR2772391A1 (fr) * 1997-12-15 1999-06-18 Toulousaine De Rech Et De Dev Procede d'alcoolyse enzymatique d'une huile de tournesol oleique, notamment pour la fabrication d'une composition lubrifiante tensioactive
EP1300470A1 (en) * 2000-07-13 2003-04-09 Nippon Suisan Kaisha, Ltd. Process for the prodcution of glycerides with lipases
WO2006077023A2 (de) * 2005-01-19 2006-07-27 Cognis Ip Management Gmbh Zusammensetzungen verwendbar als biotreibstoff

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN Bd. 009, Nr. 247 (C-307), 3. Oktober 1985 (1985-10-03) & JP 60 102192 A (MEITO SANGYO KK), 6. Juni 1985 (1985-06-06) *
PATENT ABSTRACTS OF JAPAN Bd. 015, Nr. 289 (C-0852), 23. Juli 1991 (1991-07-23) & JP 03 103499 A (MEITO SANGYO KK), 30. April 1991 (1991-04-30) in der Anmeldung erwähnt *
PATENT ABSTRACTS OF JAPAN Bd. 015, Nr. 297 (C-0854), 29. Juli 1991 (1991-07-29) & JP 03 108489 A (MEITO SANGYO KK), 8. Mai 1991 (1991-05-08) in der Anmeldung erwähnt *
PATENT ABSTRACTS OF JAPAN Bd. 015, Nr. 440 (C-0883), 11. November 1991 (1991-11-11) & JP 03 187385 A (MEITO SANGYO KK), 15. August 1991 (1991-08-15) in der Anmeldung erwähnt *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2006389A2 (en) * 2006-04-13 2008-12-24 Nippon Suisan Kaisha, Ltd. Method for production of condensed polyunsaturated fatty acid oil
EP2006389A4 (en) * 2006-04-13 2013-01-09 Nippon Suisan Kaisha Ltd METHOD FOR PRODUCING CONDENSED MULTIPLE UNSATURATED FATTY ACID OIL
US9150817B2 (en) 2006-04-13 2015-10-06 Nippon Suisan Kaisha, Ltd. Process for preparing concentrated polyunsaturated fatty acid oil
JP2009153485A (ja) * 2007-12-27 2009-07-16 Maruha Nichiro Seafoods Inc 高度不飽和脂肪酸の濃縮方法
WO2009124844A2 (en) * 2008-04-07 2009-10-15 Novozymes A/S Method for producing monounsaturated glycerides
WO2009124844A3 (en) * 2008-04-07 2010-01-07 Novozymes A/S Method for producing monounsaturated glycerides
US20110027842A1 (en) * 2008-04-07 2011-02-03 Novozymes A/S Method for Producing Monosaturated Glycerides
JP2013121366A (ja) * 2013-02-13 2013-06-20 Maruha Nichiro Seafoods Inc 高度不飽和脂肪酸の濃縮方法

Also Published As

Publication number Publication date
BRPI0606620B1 (pt) 2017-07-18
US20080045606A1 (en) 2008-02-21
WO2006077022A3 (de) 2007-01-11
BRPI0606620A2 (pt) 2009-07-07
US7935508B2 (en) 2011-05-03
JP2008526265A (ja) 2008-07-24
EP1838861A2 (de) 2007-10-03
JP4989489B2 (ja) 2012-08-01
ES2346686T3 (es) 2010-10-19
DE502006007160D1 (de) 2010-07-22
ATE470720T1 (de) 2010-06-15
EP1838861B1 (de) 2010-06-09
DE102005002711A1 (de) 2006-07-27
CA2595235A1 (en) 2006-07-27
CA2595235C (en) 2014-12-30

Similar Documents

Publication Publication Date Title
EP1838861B1 (de) Herstellung von monoglyceriden aus triglyceriden durch alkoholyse unter verwendung der thermomyces lanuginosus lipase, welche durch alkalische salze aktiviert wird
WO2006077023A2 (de) Zusammensetzungen verwendbar als biotreibstoff
DE3882852T3 (de) Herstellung von Diglyceriden.
DE60032337T2 (de) Lipasekatalysierte veresterung von fischoelen
EP1582594A2 (de) Verbessertes enzymatisches Verfahren zur Herstellung von Triglyzeriden ungesättigter Fettsäuren
DE60221199T2 (de) Konjugierte Fettsäuren enthaltende Monoglyzeride und Verfahren zu ihrer Herstellung
EP0679712B1 (en) Low safa oils
DE3853656T2 (de) Verfahren zur Umesterung von Ölen und Fetten in Anwesenheit einer Fettsäure, eines Fettsäureesters oder eines anderen Öls oder Fettes mittels einer alkalischen hoch-molekularen Lipase.
EP1978102B1 (de) Ein Gemisch enthaltend Fettsäureglyceride
DE69936757T2 (de) Verfahren zur Herstellung eines immobilisierten Enzyms
DE69000362T2 (de) Verfahren zur herstellung von triglycerid und triglyceridzusammensetzung.
DE102005037989A1 (de) Verfahren zur chemo-enzymatischen Herstellung von Fettsäureestern
DE102005057832A1 (de) Verfahren zur enzymatischen Synthese von Triglyceriden
EP1654357B1 (de) Verwendung von pit-emulsionen in enzymatischen reaktionen
EP1314775B1 (de) Verfahren zur Entsäuerung von natürlichen Fetten und Ölen
EP1322776A1 (de) Verfahren zur herstellung von glyceriden konjugierter, mehrfach ungesättigter fettsäuren aus deren alkylestern
DE3854761T2 (de) Verfahren zur herstellung von hochreiner ölsäure durch hydrolyse von sonnenblumenkernöl.
EP2298727A1 (de) Verfahren zur Herstellung von Estern kurzkettiger Alkohole aus triglyceridreichen Ölen
DE10054480A1 (de) Verfahren zur Gewinnung von 12-Hydroxystearinsäure
EP2183340A1 (de) Flüssiger biokraftstoff aus estern und gebundenen glyceriden sowie verfahren zur herstellung desselben
EP1978101A1 (de) Verfahren zur Anreicherung mehrfach ungesättigter Fettsäuren
DE19956599C2 (de) Verfahren zur Herstellung von entsäuerten Triglyceriden
EP2085469A1 (de) Lipasenformulierung
CA2987613C (en) Oil composition with mono-acylglycerides
DE69816371T2 (de) Herstellung von symmetrischen Triglyceriden aba

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006703801

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 11813939

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2007551578

Country of ref document: JP

Ref document number: 2595235

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 2006703801

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 11813939

Country of ref document: US

ENP Entry into the national phase

Ref document number: PI0606620

Country of ref document: BR

Kind code of ref document: A2